Pigments

Abstract

The present invention relates to pigments based on multicoated flake-form substrates which are distinguished by the fact that at least 8 layers [layers (A)-(H)] are on the substrate, where an SiO.sub.2 layer (=layer A) is located directly on the surface of the substrate, and to the use thereof, inter alia, in paints, surface coatings, automobile paints, powder coatings, printing inks, security printing inks, plastics, ceramic materials, glasses, paper, in toners for electrophotographic printing processes, in seed, in greenhouse sheeting and tarpaulins, as absorbers in the laser marking of paper and plastics, and in cosmetic formulations, for the preparation of pigment pastes with water, organic and/or aqueous solvents, for the preparation of pigment compositions and dry preparations.

Claims

1. A pigment based on coated flake-form substrates, which comprises at least the following 8 layers (A)-(H), on a flake-form substrate, where layer (A) is located directly on the surface of the substrate and where layers (A)-(H) are provided in the order shown and there are no intervening layers between any of layers (A)-(H): (A) a layer comprising SiO.sub.2, (B) a colourless coating having a refractive index n1.8, (C) a colourless coating having a refractive index n1.8, where layer (C) is chemically non-identical to layer (B), (D) a coloured coating having a refractive index n1.8, (E) optionally, a colourless coating having a refractive index n<1.8, (F) a colourless coating having a refractive index n1.8, (G) a colourless coating having a refractive index n1.8, where layer (G) is chemically non-identical to layer (F), (H) a coloured coating having a refractive index n1.8, and optionally (I) an outer protective layer.

2. The pigment of claim 1, wherein the flake-form substrates are selected from: natural or synthetic mica, talc, kaolin, flake-form iron or aluminium oxides, glass flakes, SiO.sub.2 flakes, TiO.sub.2 flakes, graphite flakes, synthetic support-free flakes, titanium nitride, titanium silicide, liquid crystal polymers (LCPs), holographic pigments, BiOCl and flake-form mixed oxides, or mixtures thereof.

3. The pigment of claim 1, wherein the flake-form substrates are selected from: glass flakes, natural or synthetic mica flakes or aluminium oxide flakes.

4. The pigment of claim 1, wherein the flake-form substrates are glass flakes.

5. The pigment of claim 4 wherein the glass flakes consist of window glass, calcium aluminium borosilicate glass, A glass, C glass, E glass or ECR glass.

6. The pigment of claim 1, wherein layer (A) is doped with carbon-black particles, metal particles and/or coloured pigments.

7. The pigment of claim 1, wherein layers (A) to (H) consist of oxides.

8. The pigment of claim 7 wherein the oxides are selected from: Al.sub.2O.sub.3, TiO.sub.2, ZrO.sub.2, SnO.sub.2, ZnO, Ce.sub.2O.sub.3, Fe.sub.2O.sub.3, Fe.sub.3O.sub.4, Cr.sub.2O.sub.3, CoO, Co.sub.3O.sub.4, SiO.sub.2, VO.sub.2, V.sub.2O.sub.3, NiO, titanium suboxides, or mixtures thereof.

9. The pigment of claim 1, which has an outer protective layer (I).

10. A process for the preparation of a pigment according to claim 1, comprising coating the substrate by a wet-chemical method of hydrolytic decomposition of metal salts in aqueous medium or by gas-phase coating in a fluidised-bed reactor.

11. A composition or article comprising a pigment according to claim 1 in a: paint, surface coating, automobile paint, powder coating, printing ink, security printing ink, plastic, ceramic material, glass, paper, toner for electrophotographic printing processes, seed, greenhouse sheeting or tarpaulin, absorber for the laser marking of paper or plastics, cosmetic formulation, pigment paste with water, organic and/or aqueous solvent, pigment composition, dry preparation, composition for the mass colouring of foods, composition for the colouring of coatings of food products or pharmaceutical products, or document of value.

12. A composition comprising a pigment according to claim 1.

13. The composition according to claim 12, wherein the composition comprises at least one other constituent is selected from the group consisting of: absorbents, astringents, antimicrobial substances, antioxidants, antiperspirants, antifoaming agents, antidandruff active compounds, antistatics, binders, biological additives, bleaches, chelating agents, deodorisers, emollients, emulsifiers, emulsion stabilisers, dyes, humectants, film formers, fillers, fragrances, flavours, insect repellents, preservatives, anticorrosion agents, cosmetic oils, solvents, oxidants, vegetable constituents, buffer substances, reducing agents, surfactants, propellant gases, opacifiers, UV filters and UV absorbers, denaturing agents, viscosity regulators, perfume and vitamins.

14. The pigment of claim 1, wherein: the thickness of layer (A) is 3-150 nm; the thickness of Layer (B) is 1-50 nm; the thickness of Layer (C) is 5-300 nm; the thickness of layer (D) is 1-100 nm; the thickness of layer (E), when present, is 5-500 nm; the thickness of Layer (F) is 1-50 nm; the thickness of layer (G) is 5-300 nm; and the thickness of layer (H) is 1-100 nm.

15. The pigment of claim 1, wherein: the thickness of layer (A) is 5-100; the thickness of Layer (B) is 1-30 nm; the thickness of Layer (C) is 10-200 nm; the thickness of layer (D) is 5-50 nm; the thickness of layer (E), when present, is 10-400 nm; the thickness of Layer (F) is 1-30 nm; the thickness of layer (G) is 10-200 nm; the thickness of layer (H) is 5-50 nm.

16. The pigment of claim 14, wherein the flake-form substrate has a thickness of between 0.005 and 10 m.

17. The pigment of claim 1, which has a layer (E).

18. The pigment of claim 14, which has a layer (E).

Description

EXAMPLES

(1) If the substrate employed comprises glass flakes, the chemical composition of the glass flakes is, owing to the coating with an SiO.sub.2 layer (layer (A)), of secondary importance for the further coatings and the resultant applicational properties of the final pigments. Suitable glass compositions are, for example, those as indicated in Tables 1 and 2.

(2) TABLE-US-00001 TABLE 1 Glass compositions in % Constituents Glass A Glass B SiO.sub.2 64 60 Al.sub.2O.sub.3 5 5 CaO 6.2 7.7 MgO 2.2 5.2 B.sub.2O.sub.3 5.3 6.1 Na.sub.2O + K.sub.2O 13.5 16 ZnO 3.7 0 FeO/Fe.sub.2O.sub.3 0.1 0

(3) TABLE-US-00002 TABLE 2 Glass compositions in % Constituents Glass C Glass D SiO.sub.2 65.7 64.8 Al.sub.2O.sub.3 4.0 4.9 CaO 5.9 5.6 MgO 1.9 1.7 B.sub.2O.sub.3 5.4 4.2 Na.sub.2O + K.sub.2O 12.7 14.7 ZnO 4.3 3.9 FeO/Fe.sub.2O.sub.3 0.1 0.2

Example 1

(4) 200 g of glass flakes (having a composition as described in Table 1 above under glass A, having an average flake thickness of 850 nm and a D.sub.50 value of about 80 m according to the Malvern Mastersizer 2000; manufacturer: Merck KGaA) are suspended in 2000 ml of deionised water and heated to 70 C. with stirring. The pH is adjusted to 9.0. 50 g of sodium water-glass solution (w.sub.(SiO2)=0.2) are then metered in over the course of one hour. During this addition, the pH is kept constant at 9.0 by addition of hydrochloric acid. The pH is then adjusted to 2.0 using hydrochloric acid. Next, 150 ml of an SnCl.sub.4 solution (w.sub.(SnCl4)=0.02 and w.sub.(HCl)=0.04) are added over the course of one hour. The pH is kept constant at 2.0 using sodium hydroxide solution. After completion of the metered addition of the SnCl.sub.4 solution, the pH is adjusted to 1.6 using hydrochloric acid, and the temperature of the suspension is raised to 85 C. The addition of about 200 ml of TiOCl.sub.2 solution (w.sub.(TiCl4)=400 g/l) is then begun. The metered addition is interrupted when the desired colouristic end point has been reached. The pH is kept constant during this addition using sodium hydroxide solution and is subsequently adjusted to 3.2. In the next step, 50 g of an FeCl.sub.3 solution (w.sub.(Fe)=0.10) are added over the course of 60 minutes. The pH is kept constant during this addition using NaOH and adjusted to 9.0 after completion of the metered addition of the FeCl.sub.3 solution. 160 g of sodium water-glass solution (w.sub.(SiO2)=0.2) are added at this pH. The pH is kept constant at 9.0 using hydrochloric acid. The pH is then adjusted to 2.0 using hydrochloric acid. Next, 150 ml of SnCl.sub.4 solution (w.sub.(SnCl4)=0.02 and w.sub.(HCl)=0.04) are added over the course of one hour. The pH is kept constant at 2.0 using sodium hydroxide solution. After completion of the metered addition of the SnCl.sub.4 solution, the pH is adjusted to 1.6 using hydrochloric acid. 200 ml of TiOCl.sub.2 solution (w.sub.(TiCl4)=400 g/l) are then added over the course of about 3 hours. The metered addition is interrupted when the desired colouristic end point has been reached. The pH is kept constant during this addition using sodium hydroxide solution and is subsequently adjusted to 3.2. In the final step, 50 g of FeCl.sub.3 solution (w.sub.(Fe)=0.10) are added over the course of one hour. The pH is kept constant during this addition using NaOH. After completion of the metered addition of the FeCl.sub.3 solution, the pigment suspension is filtered through a suction filter. Salt residues are washed out using deionised water. This is followed by drying overnight at 110 C. The pigment is subsequently calcined at 650 C. for 30 minutes.

Example 2

(5) 200 g of glass flakes (having a composition as described in Table 1 above under glass A, having an average flake thickness of 850 nm and a D.sub.50 value of about 80 m according to the Malvern Mastersizer 2000; manufacturer: Merck KGaA) are suspended in 2000 ml of deionised water and heated to 70 C. with stirring. The pH is adjusted to 9.0. 50 g of sodium water-glass solution (w.sub.(SiO2)=0.2) are then metered in over the course of one hour. During this addition, the pH is kept constant at 9.0 by addition of hydrochloric acid. The pH is then adjusted to 2.0 using hydrochloric acid. 28 g of an AlCl.sub.3 solution (w.sub.(AlCl3)=0.29) are subsequently added over the course of 10 minutes. Next, 150 ml of an SnCl.sub.4 solution (w.sub.(SnCl4)=0.02 and w.sub.(HCl)=0.04) are added over the course of one hour. The pH is kept constant at 2.0 using sodium hydroxide solution. After completion of the metered addition of the SnCl.sub.4 solution, the pH is adjusted to 1.6 using hydrochloric acid, and the temperature of the suspension is raised to 85 C. The addition of about 200 ml of TiOCl.sub.2 solution (w.sub.(TiCl4)=400 g/l) is then begun. The metered addition is interrupted when the desired colouristic end point has been reached. The pH is kept constant during this addition using sodium hydroxide solution and is subsequently adjusted to 3.2. In the next step, 50 g of an FeCl.sub.3 solution (w.sub.(Fe)=0.10) are added over the course of 60 minutes. The pH is kept constant during this addition using NaOH and adjusted to 9.0 after completion of the metered addition of the FeCl.sub.3 solution. 160 g of sodium water-glass solution (w.sub.(SiO2)=0.2) are added at this pH. The pH is kept constant at 9.0 using hydrochloric acid. The pH is then adjusted to 2.0 using hydrochloric acid. Next, 150 ml of SnCl.sub.4 solution (w.sub.(SnCl4)=0.02 and w.sub.(HCl)=0.04) are added over the course of one hour. The pH is kept constant at 2.0 using sodium hydroxide solution. After completion of the metered addition of the SnCl.sub.4 solution, the pH is adjusted to 1.6 using hydrochloric acid. 200 ml of TiOCl.sub.2 solution (w.sub.(TiCl4)=400 g/l) are then added over the course of about 3 hours. The metered addition is interrupted when the desired colouristic end point has been reached. The pH is kept constant during this addition using sodium hydroxide solution and is subsequently adjusted to 3.2. In the final step, 50 g of FeC.sub.3 solution (w.sub.(Fe)=0.10) are added over the course of one hour. The pH is kept constant during this addition using NaOH. After completion of the metered addition of the FeCl.sub.3 solution, the pigment suspension is filtered through a suction filter. Salt residues are washed out using deionised water. This is followed by drying overnight at 110 C. The pigment is subsequently calcined at 650 C. for 30 minutes.

Example 3

(6) 200 g of glass flakes (having a composition as described in Table 1 above under glass A, having an average flake thickness of 850 nm and a D.sub.50 value of about 80 m according to the Malvern Mastersizer 2000; manufacturer: Merck KGaA) are suspended in 2000 ml of deionised water and heated to 70 C. with stirring. The pH is adjusted to 9.0. 200 g of sodium water-glass solution (w.sub.(SiO2)=0.2) are then metered in over the course of four hours. During this addition, the pH is kept constant at 9.0 by addition of hydrochloric acid. The pH is then adjusted to 2.0 using hydrochloric acid. Next, 150 ml of an SnCl.sub.4 solution (w.sub.(SnCl4)=0.02 and w.sub.(HCl)=0.04) are added over the course of one hour. The pH is kept constant at 2.0 using sodium hydroxide solution. After completion of the metered addition of the SnCl.sub.4 solution, the pH is adjusted to 1.6 using hydrochloric acid, and the temperature of the suspension is raised to 85 C. The addition of about 200 ml of TiOCl.sub.2 solution (w.sub.(TiCl4)=400 g/l) is then begun. The metered addition is interrupted when the desired colouristic end point has been reached. The pH is kept constant during this addition using sodium hydroxide solution and is subsequently adjusted to 3.2. In the next step, 50 g of an FeCl.sub.3 solution (w.sub.(Fe)=0.10) are added over the course of 60 minutes. The pH is kept constant during this addition using NaOH and adjusted to 9.0 after completion of the metered addition of the FeCl.sub.3 solution. 160 g of sodium water-glass solution (w.sub.(SiO2)=0.2) are added at this pH. The pH is kept constant at 9.0 using hydrochloric acid. The pH is then adjusted to 2.0 using hydrochloric acid. Next, 150 ml of SnCl.sub.4 solution (w.sub.(SnCl4)=0.02 and w.sub.(HCl)=0.04) are added over the course of one hour. The pH is kept constant at 2.0 using sodium hydroxide solution. After completion of the metered addition of the SnCl.sub.4 solution, the pH is adjusted to 1.6 using hydrochloric acid. 200 ml of TiOCl.sub.2 solution (w.sub.(TiCl4)=400 g/l) are then added over the course of about 3 hours. The metered addition is interrupted when the desired colouristic end point has been reached. The pH is kept constant during this addition using sodium hydroxide solution and is subsequently adjusted to 3.2. In the final step, 50 g of FeCl.sub.3 solution (w.sub.(Fe)=0.10) are added over the course of one hour. The pH is kept constant during this addition using NaOH. After completion of the metered addition of the FeCl.sub.3 solution, the pigment suspension is filtered through a suction filter. Salt residues are washed out using deionised water. This is followed by drying overnight at 110 C. The pigment is subsequently calcined at 650 C. for 30 minutes.

Example 4

(7) 200 g of glass flakes (having a composition as described in Table 2 above under glass C, having an average flake thickness of 850 nm and a D.sub.50 value of about 80 m according to the Malvern Mastersizer 2000; manufacturer: Merck KGaA) are suspended in 2000 ml of deionised water and heated to 70 C. with stirring. The pH is adjusted to 9.0. 50 g of sodium water-glass solution (w.sub.(SiO2)=0.2) are then metered in over the course of one hour. During this addition, the pH is kept constant at 9.0 by addition of hydrochloric acid. The pH is then adjusted to 2.0 using hydrochloric acid. Next, 150 ml of an SnCl.sub.4 solution (w.sub.(SnCl4)=0.02 and w.sub.(HCl)=0.04) are added over the course of one hour. The pH is kept constant at 2.0 using sodium hydroxide solution. After completion of the metered addition of the SnCl.sub.4 solution, the pH is adjusted to 1.6 using hydrochloric acid, and the temperature of the suspension is raised to 85 C. The addition of about 200 ml of TiOCl.sub.2 solution (w.sub.(TiCl4)=400 g/l) is then begun. The metered addition is interrupted when the desired colouristic end point has been reached. The pH is kept constant during this addition using sodium hydroxide solution and is subsequently adjusted to 3.2. In the next step, 50 g of an FeCl.sub.3 solution (w.sub.(Fe)=0.10) are added over the course of 60 minutes. The pH is kept constant during this addition using NaOH and adjusted to 9.0 after completion of the metered addition of the FeCl.sub.3 solution. 160 g of sodium water-glass solution (w.sub.(SiO2)=0.2) are added at this pH. The pH is kept constant at 9.0 using hydrochloric acid. The pH is then adjusted to 2.0 using hydrochloric acid. Next, 150 ml of SnCl.sub.4 solution (w.sub.(SnCl4)=0.02 and w.sub.(HCl)=0.04) are added over the course of one hour. The pH is kept constant at 2.0 using sodium hydroxide solution. After completion of the metered addition of the SnCl.sub.4 solution, the pH is adjusted to 1.6 using hydrochloric acid. 200 ml of TiOCl.sub.2 solution (w.sub.(TiCl4)=400 g/l) are then added over the course of about 3 hours. The metered addition is interrupted when the desired colouristic end point has been reached. The pH is kept constant during this addition using sodium hydroxide solution and is subsequently adjusted to 3.2. In the final step, 50 g of FeCl.sub.3 solution (w.sub.(Fe)=0.10) are added over the course of one hour. The pH is kept constant during this addition using NaOH. After completion of the metered addition of the FeCl.sub.3 solution, the pigment suspension is filtered through a suction filter. Salt residues are washed out using deionised water. This is followed by drying overnight at 110 C. The pigment is subsequently calcined at 650 C. for 30 minutes.

Example 5

(8) 200 g of synthetic mica are coated analogously to Example 4.

Example 6

(9) 200 g of Al.sub.2O.sub.3 flakes are coated analogously to Example 4.

USE EXAMPLES

Example A1

Shower Gel

(10) TABLE-US-00003 Raw material INCI [%] A Ronastar Golden Sparks (1) CALCIUM ALUMINUM BOROSILICATE, 0.05 SILICA, CI 77891 (TITANIUM DIOXIDE), TIN OXIDE Pigment according to (1) 0.10 Example 1 Keltrol CG-SFT (2) XANTHAN GUM 1.10 Water, demineralised WATER, AQUA (WATER) 54.90 B Plantacare 2000 UP (3) DECYL GLUCOSIDE 20.00 Texapon ASV 50 (3) SODIUM LAURETH SULFATE, SODIUM 3.60 LAURETH-8, SULFATE, MAGNESIUM LAURETH SULFATE, MAGNESIUM LAURETH-8 SULFATE, SODIUM OLETH, SULFATE, MAGNESIUM OLETH SULFATE Bronidox L (3) PROPYLENE GLYCOL 0.30 5-BROMO-5-NITRO-1,3-DIOXANE Frag 280851 Fruit Cocktail (4) PARFUM 0.20 0.1% Sicovit Qulnoline (5) AQUA (WATER), WATER, CI 47005 8.30 Yellow 70 E 104 in water (ACID YELLOW 3), ACID YELLOW 3 0.1% Dragocolor True Blue (6) AQUA (WATER), WATER, CI 42090 1.30 in water (FD&C BLUE NO. 1), FD&C BLUE NO. 1 C Citric acid monohydrate (1) CITRIC ACID 0.15 Water, demineralised WATER, AQUA (WATER) 10.00 Preparation: Phase A: Introduce the water into the reactor and stir in the pigment. Slowly scatter in the Keltrol CG-SFT with stirring and stir until it has completely dissolved (do not homogenise). Add the constituents of phase B individually to phase A. Dissolve the citric acid monohydrate in water and add to the batch and stir slowly until everything is homogeneously distributed. Adjust the pH to 6.0-6.5 with addition of citric acid (if required). Sources of supply: (1) Merck KGaA/Rona (2) C. P. Kelco (3) Cognis GmbH (4) Drom (5) BASF AG (6) Symrise

Example A2

Eye Shadow

(11) TABLE-US-00004 Raw material INCI [%] A Pigment according to (1) 25.00 Example 3 Timiron (1) CI 77891(TITANIUM DIOXIDE), 5.00 Splendid Gold MICA, SILICA Talc (1) TALC 49.50 Potato starch (2) POTATO STARCH, SOLANUM 7.50 TUBEROSUM (POTATO STARCH) Magnesium stearate (1) MAGNESIUM STEARATE 2.50 B Isopropyl stearate (3) ISOPROPYL STEARATE 9.34 Cetyl palmitate (1) CETYL PALMITATE 0.53 Ewalin 1751 (4) PETROLATUM 0.53 Elegance + 79228 (5) PARFUM 0.20 D MF perfume oil Propyl (1) PROPYLPARABEN 0.10 4-hydroxybenzoate Preparation: Combine and pre-mix the constituents of phase A. Subsequently add the molten phase B dropwise to the powder mixture with stirring. The powders are transferred into powder pans of large diameter and pressed at 80 bar. Sources of supply: (1) Merck KGaA/Rona (2) Suedstaerke GmbH (3) Cognis GmbH (4) H. Erhard Wagner GmbH (5) Symrise

Example A3

Day Cream (O/W)

(12) TABLE-US-00005 Raw material INCI [%] A Ronasphere LDP (1) SILICA, CI 77891 (TITANIUM DIOXIDE), CI 5.00 77491 (IRON OXIDES) Pigment according to (1) 0.10 Example 2 Veegum HV (2) MAGNESIUM ALUMINUM SILICATE 1.00 Karion F liquid (1) SORBITOL 3.00 Methyl 4-hydroxybenzoate (1) METHYLPARABEN 0.18 Water, demineralised AQUA (WATER) 56.34 B Arlacel 165 VP (3) GLYCERYL STEARATE, PEG-100 5.00 STEARATE Lanette O (4) CETEARYL ALCOHOL 1.50 Miglyol 812 N (5) CAPRYLIC/CAPRIC TRIGLYCERIDE 7.00 Shea butter solid (6) BUTYROSPERMUM PARKII (SHEA 2.00 BUTTER) Cetiol SN (4) CETEARYL ISONONANOATE 7.00 Eutanol G (4) OCTYLDODECANOL 7.50 Emulgade PL 68/50 (4) CETEARYL ALCOHOL, CETEARYL 2.00 GLUCOSIDE Propyl 4-hydroxybenzoate (1) PROPYLPARABEN 0.08 C Perfume oil 200 530 (7) PARFUM 0.20 Dow Corning 345 (8) CYCLOMETHICONE 2.00 Euxyl K 400 (9) PHENOXYETHANOL, METHYLDIBROMO, 0.10 GLUTARONITRILE Citric acid monohydrate (1) CITRIC ACID 0.00 Preparation: Warm phase B until the solution is clear. Disperse the Veegum in the water of phase A, add the remaining raw materials, heat to 80 C. and add phase B. Homogenise phases A/B. Cool to 40 C. with stirring and add phase C. Cool to room temperature and adjust to pH 6.0. Sources of supply: (1) Merck KGaA/Rona (2) Vanderbilt (3) Uniqema (4) Cognis GmbH (5) Sasol Germany GmbH (6) H. Erhard Wagner GmbH (7) Fragrance Resources (8) Dow Corning (9) Schlke & Mayr GmbH

Example A4

Sparkling Body Cream (O/W)

(13) TABLE-US-00006 Raw material INCI [%] A Ronastar Golden (1) CALCIUM ALUMINUM 1.00 Sparks BOROSILICATE, SILICA, CI 77891(TITANIUM DIOXIDE), TIN OXIDE Pigment according to (1) 1.00 Example 1 Water, demineralised WATER, AQUA (WATER) 40.60 Carbopol Ultrez 21 (2) ACRYLATES/C10-30 ALKYL 0.60 ACRYLATE CROSSPOLYMER Citric acid monohydrate (1) CITRIC ACID 0.00 B Water, demineralised WATER, AQUA (WATER) 26.35 1,2-Propanediol (1) PROPYLENE GLYCOL 3.00 RonaCare allantoin (1) ALLANTOIN 0.20 C Paraffin liquid (1) PARAFFINUM LIQUIDUM 10.00 (MINERAL OIL), MINERAL OIL Cetiol V (3) DECYL OLEATE 6.00 Hostaphat KL 340 D (4) TRILAURETH-4 PHOSPHATE 3.00 Cetyl alcohol (1) CETYL ALCOHOL 2.00 Phenonip (5) PHENOXYETHANOL, 0.50 BUTYLPARABEN, ETHYLPARABEN, PROPYLPARABEN, METHYLPARABEN D Water, demineralised WATER, AQUA (WATER) 3.50 Triethanolamine TRIETHANOLAMINE 0.35 E Germall 115 (6) IMIDAZOLIDINYL UREA 0.30 Vogue perfume oil (7) PARFUM 0.10 Water, demineralised WATER, AQUA (WATER) 1.50 Preparation: Disperse the pearlescent pigment in the water of phase A. If necessary, acidify using a few drops of citric acid in order to reduce the viscosity. Scatter in the Carbopol with stirring. When completely dissolved, slowly stir in the pre-dissolved phase B. Heat phases A/B and phase C to 80 C., stir phase C into phases A/B, homogenise, neutralise with phase D, homogenise again and cool with stirring. Dissolve the Germall 115 in the water of phase E at 40 C. and add with stirring. Then add the perfume oil and cool to room temperature with stirring. Sources of supply: (1) Merck KGaA/Rona (2) Noveon (3) Cognis GmbH (4) Clariant GmbH (5) Nipa Laboratorien GmbH (6) ISP Global Technologies (7) Drom

Example A5

Creamy Eye Shadow

(14) TABLE-US-00007 Raw material INCI [%] A Pigment according to (1) 20.00 Example 3 Micronasphere M (1) MICA, SILICA 6.00 Unipure Green LC 789 (2) CI 77289 (CHROMIUM 4.00 CF HYDROXIDE GREEN) B Crodamol PMP (3) PPG-2 MYRISTYL ETHER 37.80 PROPIONATE Syncrowax HGLC (3) C18-36 ACID TRIGLYCERIDE 10.00 Syncrowax HRC (3) TRIBEHENIN 3.00 Miglyol 812 N (4) CAPRYLIC/CAPRIC 14.00 TRIGLYCERIDE Stearic acid (1) STEARIC ACID 3.00 Antaron V-216 (5) PVP/HEXADECENE COPOLYMER 2.00 Oxynex K liquid (1) PEG-8, TOCOPHEROL, 0.10 ASCORBYL PALMITATE, ASCORBIC ACID, CITRIC ACID Propyl 4- (1) PROPYLPARABEN 0.10 hydroxybenzoate Preparation: Heat phase B to about 80 C. until everything has melted and cool to 65 C. The pearlescent pigment, the Micronasphere and the ground chromium oxide of phase A are then added with stirring. The eye shadow is packaged at 65 C. Sources of supply: (1) Merck KGaA/Rona (2) Les Colorants Wackherr (3) Croda GmbH (4) Sasol Germany GmbH (5) ISP Global Technologies

Example A6

Hair Styling Gel

(15) TABLE-US-00008 Raw material INCI [%] A Ronastar Golden (1) CALCIUM ALUMINUM 2.55 Sparks BOROSILICATE, CI 77891 (TITANIUM DIOXIDE), SILICA, TIN OXIDE Pigment according to (1) 0.10 Example 2 Carbopol Ultrez 21 (2) ACRYLATES/C10-30 ALKYL 0.90 ACRYLATE CROSSPOLYMER Water, demineralised WATER, AQUA (WATER) 50.35 B Luviskol K 30 powder (3) PVP 2.00 Germaben II (4) PROPYLENE GLYCOL, 1.00 DIAZOLIDINYL UREA, METHYLPARABEN, PROPYLPARABEN Triethanolamine extra (1) TRIETHANOLAMINE 2.16 pure Water, demineralised WATER, AQUA (WATER) 40.94 Preparation: Disperse the pearlescent pigments in the water of phase A and scatter in the Carbopol with stirring. When completely dissolved, slowly stir in the pre-dissolved phase B. Sources of supply: (1) Merck KGaA/Rona (2) Noveon (3) BASF AG (4) ISP Global Technologies

Example A7

Shampoo

(16) TABLE-US-00009 Raw material INCI [%] A Pigment according to (1) 0.20 Example 1 Carbopol ETD 2020 (2) ACRYLATES/C10-30 ALKYL 0.90 ACRYLATE CROSSPOLYMER Water, demineralised AQUA (WATER) 63.40 B Triethanolamine extra (1) TRIETHANOLAMINE 0.90 pure Water, demineralised AQUA (WATER) 10.00 C Plantacare 2000 UP (3) DECYL GLUCOSIDE 20.00 Texapon ASV 50 (3) SODIUM LAURETH SULFATE, 4.35 SODIUM LAURETH-8 SULFATE, MAGNESIUM LAURETH SULFATE, MAGNESIUM LAURETH-8 SULFATE, SODIUM OLETH SULFATE, MAGNESIUM OLETH SULFATE Bronidox L (3) PROPYLENE GLYCOL, 0.20 5-BROMO-5-NITRO-1,3-DIOXANE Perfume oil 200 524 (4) PARFUM 0.05 Dye solution (q.s.) 0.00 Preparation: For phase A, stir the pigment into the water. Acidify using a few drops of citric acid (10%) in order to reduce the viscosity and slowly scatter in the Carbopol with stirring. When completely dissolved, slowly add phase B. The constituents of phase C are then added successively. Adjust the pH to 6.0-6.5. Sources of supply: (1) Merck KGaA/Rona (2) Noveon (3) Cognis GmbH (4) Fragrance Resources

Example A8

Shimmering Body Powder

(17) TABLE-US-00010 Raw material INCI [%] A Pigment according to (1) 10.00 Example 1 B Microna Matte Red (1) CI 77491 (IRON OXIDES), MICA 1.00 Microna Matte (1) MICA, CI 77492 (IRON OXIDES) 1.00 Yellow Ronasphere LDP (1) SILICA, CI 77891 4.00 (TITANIUM DIOXIDE), CI 77491 (IRON OXIDES) Talc (1) TALC 25.00 Glass flakes (1) CALCIUM ALUMINUM 15.00 BOROSILICATE White clay (1) KAOLIN 14.70 Mica M (1) MICA 15.00 Silk mica (1) MICA 9.50 Propyl (1) PROPYLPARABEN 0.30 4-hydroxybenzoate C Cetiol SQ (2) SQUALANE 2.00 Miglyol 812 N (3) CAPRYLIC/CAPRIC 2.00 TRIGLYCERIDE RonaCare tocopherol (1) TOCOPHERYL ACETATE 0.20 acetate Perfume (4) PARFUM 0.30 Preparation: Weigh out all constituents of phase B together and grind homogeneously in a mixer. Subsequently add phase C and continue mixing, then add phase A and grind briefly until the pearlescent pigment is uniformly distributed. Sources of supply: (1) Merck KGaA/Rona (2) Cognis GmbH (3) Sasol Germany GmbH (4) Symrise

Example A9

Long-Lasting Lip Gloss

(18) TABLE-US-00011 Raw material INCI [%] A Pigment according to (1) 4.00 Example 1 Ronastar Golden Sparks (1) CALCIUM ALUMINUM BOROSILICATE, 6.00 SILICA, CI 77891 (TITANIUM DIOXIDE), TIN OXIDE B Indopol H 100 (2) POLYBUTENE 30.00 Jojoba Glaze LV (3) SIMMONDSIA CHINENSIS (JOJOBA), 20.00 JOJOBA, SEED OIL, ETHYLENE/PROPYLENE/STYRENE COPOLYMER, BUTYLENE/ETHYLENE/STYRENE COPOLYMER Jojoba Glaze HV (3) SIMMONDSIA CHINENSIS (JOJOBA), 10.00 JOJOBA, SEED OIL, ETHYLENE/PROPYLENE/STYRENE COPOLYMER, BUTYLENE/ETHYLENE/STYRENE COPOLYMER Castor oil (4) CASTOR OIL, RICINUS COMMUNIS 23.15 (CASTOR OIL) Beeswax bleached (1) BEESWAX, CERA ALBA (BEESWAX) 4.00 Propyl 4-hydroxybenzoate (1) PROPYLPARABEN 0.10 Oxynex K liquid (1) PEG-8, TOCOPHEROL, ASCORBYL 0.05 PALMITATE, ASCORBIC ACID, CITRIC ACID Jaune Covapate W 1761 (5) RICINUS COMMUNIS (CASTOR OIL), CI 1.00 19140 (FD&C YELLOW No. 5 ALUMINUM LAKE) C Neosil CT11 (6) SILICA 1.50 Tendresse 75418C (7) PARFUM 0.20 fragrance Preparation: Weigh out all constituents of phase B together, heat to 80 C. and stir well. Stir in the pigments of phase A, scatter in the Neosil with stirring and finally add the perfume. Transfer the homogeneous mixture into containers. Sources of supply: (1) Merck KGaA/Rona (2) BP Lavera Sud (3) Desert Whale (4) Henry Lamotte GmbH (5) Les Colorants Wackherr (6) Ineos Silicas Limited (7) Symrise

Example A10

Nail Varnish

(19) TABLE-US-00012 Raw material INCI [%] Pigment (1) 1.75 according to Example 1 Ronastar (1) CALCIUM ALUMINUM BOROSILICATE, 0.25 Golden Sparks SILICA, CI 77891 (TITANIUM DIOXIDE), TIN OXIDE Thixotropic (2) BUTYL ACETATE, ETHYL ACETATE, 98.00 nail varnish NITROCELLULOSE, ACETYL base 155 TRIBUTYL CITRATE, PHTHALIC ANHYDRIDE/TRIMELLITIC ANHYDRIDE/GLYCOLS COPOLYMER, ISOPROPYL ALCOHOL, STEARALKONIUM HECTORITE, ADIPIC ACID/FUMARIC ACID/PHTHALIC ACID/TRICYCLODECANE DIMETHANOL COPOLYMER, CITRIC ACID Preparation: The pigments are weighed out together with the varnish base, mixed well by hand using a spatula and subsequently stirred at 1000 rpm for 10 min. Sources of supply: (1) Merck KGaA/Rona (2) Durlin/Bergerac NC

Example A11

Volume Mascara (O/W)

(20) TABLE-US-00013 Raw material INCI [%] A Mica Black (1) CI 77499 (IRON OXIDES), MICA, CI 5.00 77891 (TITANIUM DIOXIDE) Colorona (1) MICA, CI 77491 (IRON OXIDES), CI 3.00 Red Brown 77891 (TITANIUM DIOXIDE) Pigment according (1) 2.00 to Example 2 Satin mica (1) MICA 2.00 B Dermacryl 79 (2) ACRYLATES/OCTYLACRYLAMIDE 3.50 COPOLYMER Beeswax bleached (1) BEESWAX, CERA ALBA 3.00 (BEESWAX) Syncrowax HRC (3) TRIBEHENIN 3.50 Stearic acid (1) STEARIC ACID 5.00 Tegin M (4) GLYCERYL STEARATE 3.50 Tegosoft CT (4) CAPRYLIC/CAPRIC TRIGLYCERIDE 2.50 Dow Corning 556 (5) PHENYL TRIMETHICONE 2.00 RonaCare (1) TOCOPHERYL ACETATE 0.50 tocopherol acetate Phenonip (6) PHENOXYETHANOL, 0.80 BUTYLPARABEN, ETHYLPARABEN, PROPYLPARABEN, METHYLPARABEN C Water, WATER, AQUA (WATER) 59.15 demineralised AMP Ultra PC 1000 (7) AMINOMETHYL PROPANOL 1.25 1,3-Butanediol (1) BUTYLENE GLYCOL 1.00 RonaCare (1) UREA, DISODIUM PHOSPHATE, 0.50 Biotin Plus BIOTIN, CITRIC ACID D Germall 115 (8) IMIDAZOLIDINYL UREA 0.30 Water, WATER, AQUA (WATER) 1.50 demineralised Preparation: Melt all constituents of phase B apart from the Dermacryl 79 together at about 85 C., add the Dermacryl 79 with stirring and leave to stir for 20 min until everything is homogeneously distributed. Heat the constituents of phase C to about 85 C. Stir the pearlescent pigments of phase A into phase C. Add phase C to phase B, continue stirring and homogenise at 8000 rpm for 1 min using the Ultra-Turrax T25. Allow to cool with stirring and add phase D at 40 C. Sources of supply: (1) Merck KGaA/Rona (2) National Starch & Chemical (3) Croda GmbH (4) Degussa-Goldschmidt AG (5) Dow Corning (6) Nipa Laboratorien GmbH (7) Angus Chemie GmbH (8) ISP Global Technologies

Example A12

Tinted Day Cream with UV Protection (O/W)

(21) TABLE-US-00014 Raw material INCI [%] A Eusolex 2292 (1) ETHYLHEXYL 3.00 METHOXYCINNAMATE, BHT Eusolex 4360 (1) BENZOPHENONE-3 3.00 Arlacel 165 VP (2) GLYCERYL STEARATE, PEG-100 5.00 STEARATE Eusolex HMS (1) HOMOSALATE 5.00 Arlacel 165 VP (2) GLYCERYL STEARATE, PEG-100 3.00 STEARATE Montanov 68 (3) CETEARYL ALCOHOL, CETEARYL 3.00 GLUCOSIDE Dow Corning 345 (4) CYCLOMETHICONE 0.50 Eutanol G (5) OCTYLDODECANOL 2.00 Propyl 4- (1) PROPYLPARABEN 0.05 hydroxybenzoate B Eusolex (1) TITANIUM DIOXIDE, ALUMINA, 3.00 T-2000 SIMETHICONE Extender W (1) MICA, CI 77891 (TITANIUM DIOXIDE) 4.00 Microna (1) MICA, CI 77492 (IRON OXIDES) 2.00 Matte Yellow Microna (1) MICA, CI 77491 (IRON OXIDES) 0.20 Matte Orange Microna (1) CI 77491 (IRON OXIDES), MICA 0.20 Matte Red Microna (1) CI 77499 (IRON OXIDES), MICA 0.20 Matte Black Pigment (1) 2.00 according to Example 2 Karion FP, liquid (1) SORBITOL 5.00 RonaCare (1) ALLANTOIN 0.50 allantoin Keltrol T (6) XANTHAN GUM 0.20 Chemag 2000 (7) IMIDAZOLIDINYL UREA 0.30 Euxyl K 400 (8) PHENOXYETHANOL, 0.10 METHYLDIBROMO GLUTARONITRILE Methyl 4- (1) METHYLPARABEN 0.15 hydroxybenzoate Water, AQUA (WATER) 57.60 demineralised Preparation: Disperse all constituents apart from the Keltrol T in the water of phase B. Scatter the Keltrol into phase B with stirring and heat to 80 C. after 15 minutes. Heat phase A to 75 C. Slowly stir phase B into phase A and homogenise. Cool with stirring. Sources of supply: (1) Merck KGaA/Rona (2) Uniqema (3) Seppic (4) Dow Corning (5) Cognis GmbH (6) C. P. Kelco (7) Chemag AG (8) Schlke & Mayr GmbH

Example A13

Cream Conditioner

(22) TABLE-US-00015 Raw material INCI % A Water Aqua (water) 79.7 Pigment according to (1) 0.50 Example 2 Luviquat Hold (2) Polyquaternium-46 5.00 Luviquat PQ 11 (2) Polyquaternium-11 2.00 1,3-Butanediol (1) Butylene Glycol 3.00 B Cremophor A 6 (2) Ceteareth-6 and Stearyl Alcohol 3.00 Ammonyx 4 (2) Stearalkonium Chloride 3.00 Lanette wax O (3) Cetearyl Alcohol 2.00 Eusolex 2292 (1) Octyl Methoxycinnamate 0.10 C RonaCare (1) Tocopheryl Acetate 0.50 tocopherol acetate RonaCare (1) Bisabolol 0.10 bisabolol nat. Perfume Parfum 0.10 Germaben II (4) Propylene Glycol, Diazolidinyl Urea, 1.00 Methylparaben, Propylparaben Preparation: Disperse the pigments in the water of phase A and add the remaining raw materials. Stir after each addition and subsequently heat to 75 C. Mix the raw materials of phase B, heat to 75-80 C. and add to phase A. Mix until a homogeneous distribution is present. Add phase C at 45 C. Sources of supply: (1) Merck KGaA/Rona (2) BASF AG (3) Cognis GmbH (4) ISP Global Technologies

Example A14

Production of Hard Caramels

(23) TABLE-US-00016 Raw material % Sugar (3) 41.0 Water Aqua (Water) 17.118 Glucose syrup (2) C* Sweet 41.0 Pigment according (1) (0.1% based on casting composition) 0.082 to Example 1 E 104 dil. 1:100 (4) Sikovit 0.4 Aroma (5) Banane 9/030388 0.4 Sources of supply: (1) Merck KGaA (2) Cerestar, Krefeld (3) Sdzucker (4) BASF, Ludwigshafen (5) Dragaco, Holzminden The sugar is heated to 100 C. with the water and the glucose syrup is then added. The solution is subsequently heated to 145 C. After addition of the gold pigment, the colour solution and the aroma, the caramel solution is poured into greased moulds using a funnel. Finally, the mixture is allowed to cool for two hours. The gold pigment can either be mixed with the sugar or added as a mixture with the glucose syrup. This variant comprises no acid since this would cause the caramelisation to be excessive.

Example A15

Coating of Tablets

(24) a) Initial weight 1 kg of white tablets d=8 mm, G=200 mg

(25) TABLE-US-00017 Raw material % Sepifilm Lp 10 (3) Mixture of 6.0 Hydroxypropylmethylcellulose, Stearic Acid and Microcrystalline Cellulose Pigment according to (1) 5.0 Example 2 Water Aqua (Water) 89.0 Sources of supply: (1) Merck KGaA (2) Seppic Total application amount: 200 g This corresponds to 1.2 mg of polymer/cm.sup.2 of tablet surface. Preparation of the film-coating solution: The gold pigment is stirred into the water. Additional dyes are subsequently added. Finally, the film former (HPMC) is scattered into the suspension. Due to the increasing viscosity, the stirring speed must also be increased correspondingly. After about 40-60 minutes, the HPMC has completely dissolved and the solution can then be sprayed onto the tablets. The spray application is carried out by means of standard coating methods.